The isotope-enabled general circulation models (GCM) have been widely applied to simulate the variability of stable isotopes in meteoric water at various time scales. The in-situ observations of water vapour isotopes are an important basis for assessing the performance of isotope-enabled GCMs, although they are still limited. Here we compiled the observations of near-surface water vapour isotopes on a daily scale at 17 stations in East Asia, and assessed the skill and the association between isotope error and meteorological errors on a daily scale. Generally, the spatial pattern and seasonal variability can be well simulated in the isotope-enabled GCMs. The models show better skill for warm and humid backgrounds, which also corresponds to the monsoonal regions with lower latitudes in East Asia. As spatial resolution is finer, the skill of models is better, which can be seen from the two GCMs. According to the correlation coefficient, the improvement of resolution is more obvious in summer than in winter, especially for IsoGSM. In addition, the correlation coefficient in winter is usually larger than that in summer. The daily modelling has good potential to investigate the daily or synoptic climate information in water isotopes. The findings are useful for understanding the applicability of isotope-enabled models in East Asia and the climate factors influencing the skill of isotope-enabled models on a daily basis.

Global warming has accelerated the degradation of permafrost and glaciers on the Tibetan Plateau, resulting in a substantial release of meltwater that is affecting the regional ecosystem. Despite the significant environmental effects of meltwater, there is a lack of comprehensive studies on the historical changes in meltwater. The key is to obtain reliable quantitative records of meltwater changes. Here, we present Holocene delta Dwax records from a loess and a peatland on the northeastern Tibetan Plateau, documenting the hydrogen isotopic composition of the regional summer precipitation and surface water affected by meltwater respectively. The two records together reveal substantially increased meltwater during the middle to late Holocene transition, lasting for approximately 1500 years. The meltwater event coincides with a series of exceptional warmth during 5-3 ka across the midlatitude inland Asia, suggesting that the regional warming was the primary driver of the increased meltwater. This meltwater event had a considerable influence on regional ecology, leading to dramatic fluctuations in algal and bacterial populations and biomass. In addition, this meltwater event may have occurred over a larger area of glaciers and permafrost, where the water isotope records during 5 ka and 3 ka differ from low-latitude regions. This meltwater event, as a crucial aspect of the climatic changes during the middle to late Holocene transition in inland Asia, its driving mechanism and environmental impacts warrant further investigation.

In global hydrological circulation, evaporation widely occurs from the land, the oceans, and other water surfaces. Compared to the evaporation from open water, the below-cloud evaporation of falling raindrops is more difficult to quantify. As an alternative to the traditional microphysical model, the difference in stable water isotopes between water vapour and precipitation provides a new perspective to estimate the raindrop mass loss. According to the recent observations of stable isotopes in near-surface water vapour and precipitation in five sampling stations from humid to arid climates in East Asia, we quantified the below-cloud evaporation of raindrops using both a microphysical model and an isotope inversion model. The results indicate that the isotope inversion model, relative to the microphysical model, usually underestimates the impact of below-cloud evaporation on precipitation, especially in arid inland. The sensitivity test of the two models to errors in climatic factors shows that the microphysical model was more sensitive to errors in temperature and relative humidity than the isotope inversion model. We also plot the ranges that the isotope inversion model has solutions under various meteorological and isotope inputs. The findings are useful for understanding the atmospheric processes below the cloud base and the comparability of different methods in quantifying below-cloud evaporation.

Terrestrial snails are sensitive to climate changes and their shell's oxygen isotope composition (delta O-18(shell)) is widely used in studies of paleoclimate reconstructions. However, the interpretation of delta O-18(shell) remains complex due to the combined effects from different factors such as precipitation delta O-18 (delta O-18(p)), relative humidity (RH), and temperature. Furthermore, no systematic studies have addressed the transformation of oxygen isotope signals from rainfall to the aragonite shell via snail body water. Here we present the results of Cathaica fasciola body water delta O-18 (delta O-18(BW)) and its content, which were sampled every two days throughout the growing season in 2021 in Xi'an. Meanwhile, the soil water delta O-18 (delta O-18(SW)), delta O-18(p), rainfall amount, RH and temperature were also simultaneously monitored, and two high-resolution (at similar to 0.3 mm interval) delta O-18(shell) series were obtained from two live snails collected in September and October 2021, respectively. These data reveal that the delta O-18(BW) mimic the variations of delta O-18(p), and they are positively correlated (r(2) = 0.84) for precipitation events and the correlation coefficient only increases slightly (r(2) = 0.88) when RH is included in the multivariate analysis. During non-precipitation intervals, there is an obvious negative correlation between delta O-18(BW) and RH. Moreover, the variations of two delta O-18(shell) series are broadly consistent with the theoretically calculated delta O-18(shell) from delta O-18(BW)/delta O-18(p) at seasonal scale. Collectively, this study demonstrates that delta O-18(p) is the first-order control on the seasonal variations of delta O-18(BW) and delta O-18(shell), while RH play its role during non-precipitation periods. Importantly, this study lays good foundation for reconstructing terrestrial seasonal distribution of precipitation and extreme rainfall events using fossil shells in the geological past.

Precipitation isotopic composition variations that are directly recorded in geological samples play an important role in understanding past hydroclimatic changes. In arid regions, the hydrogen isotopes of leaf wax (δDwax) in loess sections can provide records of summer precipitation isotopes. However, previous studies have primarily focused on the orbital scale, and there was still a lack of clear understanding of variations in precipitation isotopes on shorter timescales and their implications for climate change. In this study, we report centennial-resolution loess δDwax records from the central Chinese Loess Plateau (CLP) from the last deglaciation to the early Holocene. We compared the loess optically stimulated luminescence chronology and U-Th ages conveyed by linking stalagmite δ18O and loess δDwax to validate the δDwax method as a potential tool for assessing loess chronology on the suborbital scale. Our findings also indicated that regional precipitation isotopes experienced a depletion of approximately 24‰ for δD and around 3.2‰ for δ18O during the last deglaciation. The overall precipitation isotope amplitude in the central CLP was similar to that of typical East Asian monsoon regions and lower than that of the Indian monsoon and westerly regions. However, the precipitation isotope oscillations on the millennial scale in the central CLP were significantly weaker than those in eastern to central China. The finding affirmed that although the summer precipitation in the CLP was primarily influenced by the East Asian monsoon system at the orbital scale, the northern boundary of the summer rain belt remained a distance away from the interior of the CLP during the last deglaciation. As a result, the short-term oscillations of atmospheric circulation were not strongly reflected in the precipitation isotopes of the central CLP. This result highlighted spatial and temporal differences in precipitation isotope variability between the dominant and marginal regions of the East Asian monsoon system.

When hydrometeors fall from an in-cloud saturated environment toward the ground, especially in arid and semiarid regions, below-cloud processes may heavily alter the isotopic composition of precipitation through equilibrium and non-equilibrium fractionations. If these below-cloud processes are not correctly identified, they can lead to misinterpretation of the precipitation isotopic signal. To correctly understand the environmental information recorded in the precipitation isotopes, qualitatively analyzing the below-cloud processes and quantitatively calculating the below-cloud evaporation effect are two important steps. Here, based on 2 years of synchronous observations of precipitation and water vapor isotopes in Xi'an, China, we compiled a set of effective methods to systematically evaluate the below-cloud evaporation effect on local precipitation isotopic composition. The ?d?d diagram is a tool to effectively diagnose below-cloud processes, such as equilibration or evaporation, because the isotopic differences (d(2)H; d-excess) between the precipitation-equilibrated vapor and the observed vapor show different pathways. By using the AdA8 diagram, our data show that evaporation is the major below-cloud process in Xi'an, while snowfall samples retain the initial cloud signal because they are less impacted by the isotopic exchange between vapor and solid phases. Then, we chose two methods to quantitatively characterize the influence of below-cloud evaporation on local precipitation isotopic composition. One is based on the raindrop's mass change during its falling (hereafter referred to as method 1), and the other is dependent on the variations in precipitation isotopic composition from the cloud base to the ground (hereafter referred to as method 2). By comparison, we found that there are no significant differences between the two methods in evaluating the evaporation effect on 82Hp, except for snowfall events. The slope of the evaporation in proportion to the variation in d(2)H (Fi/?d(2)H) is slightly larger in method 1 (1.0 %o %(-1)) than in method 2 (0.9 %o %(-1)). Additionally, both methods indicate that the evaporation effect is weak in autumn and heavy in spring. Through a sensitivity test, we found that in two methods, relative humidity is the most sensitive parameter, while the temperature shows different effects on the two methods. Therefore, we concluded that both methods are suited to the investigation of the below-cloud evaporation effect, while in method 2, other below-cloud processes, such as supersaturation, can still be included. By applying method 2, the diagnosis of below-cloud processes and the understanding of their effects on the precipitation isotopic composition will be improved.

For samples with nitrogen isotope content between −9.9 and 19.5‰, nitrogen isotope values can be obtained directly without correction since there is no significant difference between the conventional correction method and the uncorrected method.

Atmospheric precipitation has widely taken part in the formation and accumulation of many geological archives. In these processes, the isotope fractionations are tightly related to the meteorological factors, such as temper-ature and precipitation amount. Therefore, precipitation isotopes are usually regarded as an effective proxy to reconstruct the paleoclimate and paleoenvironmental changes. However, with the deepening of research, it is found that the temperature effect is not suitable for all regions and time scales, especially in regions with complex moisture sources. Moreover, the applicable mechanism of the temperature effect is still unclear. Here, we chose Xi'an as our study site, because it is located in the transition zone of the East Asian Summer Monsoon (EASM) and the westerlies with relatively complex water vapor sources. Through conducting a three-year, high-resolution, relatively continuous water vapor isotopic composition measurements in Xi'an, we defined the duration of the EASM here, which normally starts in June and is over in September. By separating the & delta;18Op into monsoon and non-monsoon seasons, we found a significant temperature effect in the non-monsoon seasons, with a correlation coefficient of 0.54, while no temperature effect is observed in the monsoon seasons and the whole year. Our water vapor isotopic results suggested that the establishment of temperature effect of precipitation isotopes should follow two prerequisites: 1. single water vapor source; 2. large temperature gradient. Our results specify the applicable conditions of temperature effect and potentially help us to better use precipitation isotopes to understand the paleo-temperature variations in different regions.

Land snails are abundant and well preserved in loess-paleosol sequences on the Chinese Loess Plateau (CLP) and are often regarded as valuable climatic indicators in paleoclimate reconstruction. To date, many stable isotope investigations have been carried out on land snail shells (e.g., δ13Cshell and δ18Oshell) from diverse geographical and climatic regions. However, few studies have been conducted on modern minute land snails (2–10 mm) on the CLP, and their climatic significance has not been adequately understood. Here, we present new δ13Cshell and δ18Oshell data from four minute modern land snails (Pupilla aeoli, Gastrocopta armigerella, Opeas striatissimum, Vallonia tenera), and analyses of their correlations with climatic factors (growing season temperature, precipitation and relative humidity) were conducted to examine their climatic significance across the CLP. The results show that δ13Cshell can record local vegetation information and has the potential to be a reliable precipitation proxy. Interestingly, δ18Oshell exhibits spatially scattered values in the studied region, and these data yielded poor correlations with various climatic parameters, such as precipitation amount, temperature and relative humidity. Given the similar spatial characteristics of observed precipitation δ18O (δ18Op), these phenomena may support the dominant control of δ18Op on δ18Oshell.

The chronology of geological records in lacustrine, peatland and marine sediments for the late glacial depends mainly on 14C dating technology, which provides the basic database for global paleoclimate research. However, 14C reservoir correction always challenges the accuracy of the 14C chronology of terrestrial and marine sediments and the uncertainty of the 14C chronology associated with the carbon reservoir effect becomes critical for high resolution paleoclimate studies. Here, based on the hypothesis of synchronization of precipitation isotopes, we verify and identify a series of in-phase points of precipitation isotopes (IPPIs) between sediment leaf-wax hydrogen and stalagmite-calcite oxygen isotopes. Because stalagmite oxygen isotope records are accurately dated by U–Th dating technology, the ages of stalagmite IPPIs could be used to improve 14C reservoir correction of lacustrine IPPIs. We found that reservoir-corrected 14C ages of lacustrine, peat, and marine IPPIs are scattered with an average uncertainty of 1 ka when compared with the corresponding IPPIs on U–Th age scales. We suggest that the reservoir age correction at different time intervals could be further adjusted by using the U–Th age-backed IPPIs, which largely reduces the uncertainty of the 14C chronology and thus provides more accurate paleoclimate records.

Combustion-derived water vapor (CDV) has significant impacts on urban climate and environment. However, temporal variations of contribution of CDV (CCDV) to urban humidity are unclear due to lack of observations. This study examined the temporal variations of CCDV in Xi'an during winter from 2016 to 2019. We found that the diurnal variation of CCDV is mainly controlled by atmospheric stability, but the peak of CCDV at 9 am is due to the increasing water vapor emission by motor vehicles during the morning rush hour. In addition, the monthly variation of CCDV is related to fossil fuel consumption, but the low values of CCDV in late January and early February is due to substantial decrease of energy utility because of the massive outflow of population during the Spring Festival. Our findings may be helpful for urban pollution control because CDV can play an important role in the secondary conversion of pollutants.

Atmospheric humidity has been shown to promote haze formation, but it remains unclear why the air is humid during heavy haze days in winter. Here we combine water vapor isotope measurements with WRF-Chem simulations to elucidate increasing humidity with aggravation of haze during wintertime in urban Beijing. The vapor isotopic analysis in Beijing shows that the combustion-derived water (CDW) constitutes 11.0± 6.2 % of the atmospheric moisture and its fraction in total moisture increases with aggravation of haze. Modeling results reveal that, in addition to the water vapor transported from south or east to Beijing with occurrence of haze, CDW has a considerable impact on the increasing humidity when haze becomes heavy or severe. Aerosol-radiation interactions generally decrease the water vapor content and only increase humidity with occurrence of severe haze with hourly PM2.5 concentrations exceeding 250μg m-3. Although CDW is insignificant in the global atmospheric vapor budget, it could play an important role in modifying the local weather during haze days.

Extreme rainfall events cause tremendous threats to people’s lives and economic well-being. Given the short time span of instrumental records, reconstructing the full range of past rainfall variability using available proxies is impossible when trying to unravel the history and underlying mechanisms of extreme precipitation events. However, this work is usually limited by the temporal resolution of current paleoclimate records. Here we demonstrate that the ultra-high resolution measurements of δ18O of terrestrial snail shells of Cathaica fasciola (Draparnaud, 1801) can be used to reconstruct the rainfall variability on weather time scales. Broadly, the modern daily time resolution snail shell’s δ18O profile shows a negative trend from late March to September in 2020, which resembles the variations of monitored δ18O and amount of precipitation. Meanwhile, six abrupt negative deviations were observed in the δ18O profiles and these deviations matched well with the instrumental precipitation events for the same period. The high correlation of shell’s δ18O with rainfall amount during the six precipitation events indicates that the ultra-high resolution δ18O records of gastropod shells have the potential to qualitatively record local synoptic rainfall events. Our study highlights that the terrestrial gastropod shell could provide daily to weekly geochemical proxies and has the potential to be used as an ultra-high resolution archive for characterizing terrestrial paleoweather, such as extreme precipitation events.

Hopke and Dai (1) propose that the observed correlation between PM2.5 (concentration of particulate matter with an aerodynamic diameter ≤2.5 μm) concentration and the fraction of anthropogenic combustion-derived water (CDW) by Xing et al. (2) is likely due to local residential coal combustion (RCC). Here is our response. Hopke and Dai (1) state that “a significant fraction of the observed winter … sulfate is primary rather than secondary sulfate.” This statement is incorrect for the Guanzhong Basin and the city of Xi’an during 2016 to 2018 heating seasons. Primary sulfate contributions, both industrial and residential, have been considered in our WRF-Chem model (3), and the average secondary sulfate accounts for 74.5% of the total … [↵][1]1To whom correspondence may be addressed. Email: jjcao{at}ieecas.cn. [1]: #xref-corresp-1-1

The Chinese loess-paleosol sequences provide important archives for studying paleoenvironmental changes. However, the lack of independent and accurate time scales hinders the study between loess and other records. Asian stalagmite δ18O records indicate synchronous patterns of paleoprecipitation δ18O over large geographic regions. The record of hydrogen isotopic composition of plant wax (δDwax) in Chinese loess is also controlled by rainwater δD. Both share a common origin. The linear relationship between rainfall δ18O and δD variance provides the basis to tie together chronologies of the same climate event in different records. Here, we show a new loess chronology by correlating chronologies of marker boundaries of the prominent climate chronozones in stalagmite δ18O and summer insolation to the equivalent climate stratigraphy in the loess δDwax sequence. We first developed and tested this novel methodology with data since the last interglacial on a millennial scale, and then applied this approach to the loess δDwax sequence for the past 800 k.y. to improve the traditional chronology based on magnetic susceptibility and grain size. The new δDwax time series provides not only an improved chronology for studying paleoclimate changes during interglacial intervals, it also represents a unique database with which to better understand the links between the Asian monsoon changes in the Chinese loess and other global climate events, especially for the periods prior to 640 ka, for which stalagmite records are not available.

雾霾天气是我国近年来面临的严峻环境问题之一,它的频繁发生严重影响我国居民的日常生活和身心健康.众所周知,PM2.5(空气动力学当量直径小于等于2.5 μm的颗粒物,直径还不到头发丝粗细的1/20)是造成空气污染的一个重要因素.它的来源非常复杂,包括一次排放和二次形成颗粒物.由氮氧化物(NOx)、二氧化硫(SO2)和挥发性有机组分(VOCs)等前体物反应生成的二次颗粒物(如硝酸盐、硫酸盐、二次有机物)是PM2.5的重要组成成分.大量研究表明,由水汽作为媒介的液相化学反应是二次气溶胶生成的重要途径.水汽含量的升高将加速硫酸盐、硝酸盐及二次有机物的生成,导致雾霾过程持续和进一步恶化.

Abstract. Below-cloud evaporation effect heavily alters the initial precipitation isotopic composition, especially in the arid and semi-arid regions, and leads to misinterpreting the isotopic signal. To correctly explore the information contained in the precipitation isotopes, the first step is to qualitatively analyze the falling raindrops encountered below-cloud processes, and then to quantitatively compute the below-cloud evaporation ratio of raindrops. Here, based on two-year precipitation and water vapor isotopic observations in Xi'an, we systematically evaluated the variations of precipitation and water vapor isotopes caused by the below-cloud evaporation effect. Our results suggest that the equilibrium method could be successfully used to predict the ground-level water vapor isotopic composition in semi-arid climates, especially for the winter data. Moreover, by using △d△δ-diagram, our data showed that evaporation is the mainly happened below-cloud process of raindrops, while snowfall samples retained the initial cloud signal because of less isotopic exchange between vapor and solid phases. In terms of meteorological factors, both temperature, relative humidity, and precipitation amount affect the intensity of below-cloud evaporation. In arid and semi-arid regions, the below-cloud evaporation ratio computed by the mass conservation equation would be overestimated relative to the isotopic method, while relative humidity is the most sensitive parameter in computing the remaining fraction of evaporation. In the Chinese Loess Plateau (CLP) city, raindrops are weakly evaporated in autumn and winter, and heavily evaporated in spring and summer, and in the meantime, the evaporation intensity is related to the local relative humidity. Our work sets an integrated and effective method to evaluate the below-cloud evaporation effect, and it will improve our understanding of the information contained in precipitation isotopic signals.

Anthropogenic combustion-derived water (CDW) may accumulate in an airshed due to stagnant air, which may further enhance the formation of secondary aerosols and worsen air quality. Here we collected three-winter-season, hourly resolution, water-vapor stable H and O isotope compositions together with atmospheric physical and chemical data from the city of Xi'an, located in the Guanzhong Basin (GZB) in northwestern China, to elucidate the role of CDW in particulate pollution. Based on our experimentally determined water vapor isotope composition of the CDW for individual and weighted fuels in the basin, we found that CDW constitutes 6.2% of the atmospheric moisture on average and its fraction is positively correlated with [PM2.5] (concentration of particulate matter with an aerodynamic diameter less than 2.5 μm) as well as relative humidity during the periods of rising [PM2.5]. Our modeling results showed that CDW added additional average 4.6 μg m-3 PM2.5 during severely polluted conditions in the GZB, which corresponded to an average 5.1% of local anthropogenic [PM2.5] (average at ∼91.0 μg m-3). Our result is consistent with the proposed positive feedback between the relative humidity and a moisture sensitive air-pollution condition, alerting to the nontrivial role of CDW when considering change of energy structure such as a massive coal-to-gas switch in household heating in winter.

The hydrogen isotopic compositions (δD) of long-chain plant leaf waxes can reflect changes of continental hydrology and thus have been increasingly utilized for paleoclimate reconstruction. One of the unresolved major issues is whether variations of leaf wax δD (δDwax) signals along a precipitation gradient reflect changes of precipitation δD, precipitation amount, and/or evapo-transpiration. This ambiguity limits our interpretation of δDwax in geological records as well as the quantitative reconstruction of paleohydrological variability. Here we systematically investigated δD of soil water and waxes extracted from soil and plant leaves in the Chinese Loess Plateau (CLP) and its surrounding areas along a precipitation gradient with mean annual precipitation (MAP) varying from 140 mm to 676 mm. The results showed that while the variation of modeled precipitation δD has no significant correlation with MAP, soil water δD, soil δDwax, and individual plant δDwax exhibit negative correlations with MAP. In relatively arid areas, the δD values of soil water and plant leaf waxes are significantly more positive due to much lower precipitation relative to evapo-transpiration, suggesting that effective precipitation (P:E ratio) has played a crucial role in the D-enrichment of soil and plant leaf waxes in this region. While parallel decreasing trends in δDwax are found along the increase of precipitation gradient among dominant plants (including Artemisia spp., Aster hispidus, Stipa bungeana, and Cleistogenes squarrosa) in the region with similar slopes, the large δD offsets between plant groups suggest that plant type is an important factor in controlling plant hydrogen isotope fractionations. Our results indicate that δDwax preserved in paleosols can be used to infer past conditions of water availability in arid and semi-arid inland regions, but with a mechanism that is different from the influence of “amount effect” in humid areas. Moreover, vegetation changes should be constrained by independent paleobotanical data before monsoon related paleohydrology in the CLP and its surrounding areas can be quantitatively reconstructed using the plant wax δD proxy.

The Wei River is the largest tributary of the Yellow River in China. To understand the sources and cycling of nitrate in the Wei River, we determined the concentrations and nitrogen and oxygen isotopic values of nitrate from water samples. Our results revealed that NO3--N dominated the inorganic N and ranged from 0.1 to 8.8 mg/L (averaging 3.3 mg/L). Although this NO3--N concentration does not exceed the World Health Organization's drinking water standard of 10 mg/L, the NO3--N content of most water samples exceeded 3 mg/L, indicating poor water quality. The NO3--N concentrations and delta N-15-NO3- values demonstrate that there are significant differences in the spatial distribution of nitrogen between the tributaries and the main stream of the Wei River. In addition, a negative linear relationship (r(2) = 0.63) between NO3--N concentrations and delta O-18-NO3- values suggests mixing between two distinct sources (fertilizer and manure or sewage). Furthermore, we infer that the main source of nitrate is not manure or sewage itself, but rather the nitrification of NH4+ in manure and sewage. Finally, no obvious denitrification processes were observed. These results expand our understanding of sewage as a major source of nitrate to the Wei River, emphasizing the role of nitrification.